Lubricating oil compositions



United States Patent 3,547,820 LUBRICATING OIL COMPOSITIONS Fred E. Woodward, Plainfield, N.J., and William Katz enstein, Broomal, Pa., assignors to GAF Corporation, New York, N.Y., a corporation of Delaware No Drawing. Continuation of application Ser. No. 583,097, Sept. 29, 1966, which is a continuation-in-part of application Ser. No. 203,007, June 18, 1962, which in turn is a continuation-in-part of application Ser. No. 154,834, Nov. 24, 1961. This application Dec. 20, 1968, Ser. No. 786,848

Int. Cl. Cm 1/46 U.S. Cl. 252--32.5 8 Claims ABSTRACT OF THE DISCLOSURE A mineral lubricating oil composition containing about 0.5% to about 25% by weight of a material selected from a phosphate ester and a salt of a phosphate ester of phosphoric acid and an oxyalkylene ether of an organic hydroxy compound. The organic hydroxy compound is selected from alkyl phenols and aliphatic straight chain alcohols, the phosphate ester being selected from monoesters, diesters and mixtures thereof, the oxyalkylene group of the oxyalkylene ether comprising a maximum of about 50% by weight thereof.

This application is a streamlined continuation of application Ser. No. 583,097, filed Sept. 29, 1966, now abandoned, which in turn is a continuation-in-part of application Ser. No. 203,007 filed June 18, 1962, now abandoned, which in turn is a continuation-in-part of application Ser. No. 154,834 filed Nov. 24, 1961, now abandoned.

This invention relates to improved lubricating oil compositions, and more particularly to detergent mineral oil lubricating compositions for use in internal combustion engines, which compositions have outstanding antiwear properties.

It is well known that lubricating oils commonly used in internal combustion engines and which are derived from the refining of mineral oils undergo considerable oxidation and degradation during use in an engine. This oxidation of the oil produces sludge deposits which may cause the various parts of the engine to operate inefficiently. In order to overcome such conditions, detergent lubricating oils have been developed which have the ability to suspend the aforementioned sludge materials and keep them from interfering with the normal and efiicient operation of the engine. Other additives have been developed for use in such oil compositions to improve the lubricating characteristics thereof and thereby lessen the wear of the engine parts. The present invention is concerned with the discovery of a class of additives which exhibits not only outstanding detergent characteristics but also excellent antiwear properties.

It is therefore an object of the present invention to provide a lubricating oil composition which has outstanding detergent characteristics.

It is another object of the present invention to provide a lubricating oil composition which has excellent and improved antiwear properties.

It is still another object of the present invention to provide a mineral oil lubricating oil composition which is characterized by outstanding detergent and antiwear properties.

It is still another object of the present invention to provide a mineral oil lubricating composition particularly adaptable for use in internal combustion engines and which has improved detergent and lubricating properties.

It is still another object of the present invention to provide a mineral, oil lubricating composition particularly 3,547,820 Patented Dec. 15, 1970 adapted for use in internal combustion engines which is characterized by outstanding detergent and antiwear properties.

Other objects will appear as the description proceeds.

The compositions of the present invention comprise the usual mineral lubricating oils on the one hand which may also contain the conventional modifiers and additives in minor amounts such as synthetic lubricating oils, viscosity index improvers, corrosion inhibitors, pour depressants, dyes and the like, and a phosphate ester of a nonionic surface active agent more suificiently described below.

The phosphate esters of nonionic surface active agents which are herein contemplated are monoand diphosphate esters and mixtures thereof. The nonionic precursors for the esters are selected from the group consisting of polyoxyalkylene ethers of alkyl phenols and aliphatic alcohols of at least 15 carbon atoms, said oxyalkylene groups containing from 2 to 3 carbon atoms: each. The amount of oxyalkylene groups may vary from about 10% (i.e., derived from the interaction of 1 mole alkylene oxide) up to 50% by weight alkylene oxide. The alkylene oxides or precursors thereof which may be employed to yield the corresponding oxyalkylene groups in the nonionic surface active agent are those which contain from 2 to 3 carbon atoms such as ethylene oxide, propylene oxide, and the like. In addition, it is clear and obvious that mixtures of such oxyalkylating reagents may be used whereby there results in the nonionic surfactant, variations in the oxyalkylene groups.

The nonionic oxyalkylated products which are herein contemplated as precursors for the phosphate esters are well known in the art and are derived from alkyl phenols and aliphatic alcohols of at least 15 carbon atoms and the alkylene oxide as, for example, disclosed in U.S. Pats. 2,213,477 and 1,970,578. The following illustrate some typical suitable phenols and alcohols which may be used to form the corresponding nonionic surface active agents which are precursors for the instantly contemplated phosphate esters:

nonyl phenol (nonyl derived from propylene trimer) dodecyl phenol (derived from propylene tetramer) hexadecyl phenol octadecyl phenol,

and the like phenols containing a plurality of different alkyl groups, for example:

butyl amyl phenol butyl hexyl phenol amyl hexyl phenol amyl heptyl phenol ethyl heptyl phenol as Well as phenols containing a plurality of similar alkyls such as, in addition to those above:

di-n-hexyl phenol diisohexyl phenol di-n-heptyl phenol di-n-octyl phenol diiso-octyl phenol dinonyl phenol didodecyl phenol ditetradecyl phenol diocta decyl phenol tri-n-octyl phenol I tri-n-butyl phenol, and the like, and

alcohols prepared from olefins from C to C by the oxa process.

The above compounds are then reacted with the alkylene oxide as described above to yielcLthe nonionic surface active agents which are then used to prepare phosphate esters employed in the compositions of the present invention.

The phosphate esters may be prepared by the reaction of 1 mol of P with 2 to 4.5 mols of the nonionic surfactant as described and claimed in US. Patent 3,004,056 by Nunn and Hesse and US Patent 3,004,057 by Nunn. As described in the said Nunn and Hesse patent, the reaction between the P 'O and the nonionic polyoxyalkylene ether is conducted under substantially anhydrous conditions and at a temperature below about 110 C. In its preferred form, the reaction is carried out by adding the P 0 gradually, with vigorous agitation to the nonionic surface active agent in liquid form. The reaction is exothermic and cooling is in some cases necessary to keep the temperature below 110 C., since discolored and darkened products tend to be produced above this temperature. The reaction proceeds continuously during the addition of the P 0 and is preferably followed by maintenanceof the reaction mixture at ambient temperatures up to 1 C. for an additional period of time after completion of such addition to allow for complete solution of the P 0 and reaction with the nonionic surface active agent.

The following examples illustrate the preparation of such phosphate esters.

Example A 2.7 mols of a nonionic surface active compound derives from dinonyl phenol condensed with 4 mols of ethylene oxide is reacted with 1 mol of P 0 in the manner described in the examples of US. Pat. 3,004,056. The product consists of about equal amounts of monoand diester with about 10-15% unreacted nonionic.

Example B The procedure of Example A is repeated except that the IlOIilOniC is a dodecyl phenol plus 2 mols of ethylene oxide condensate.

Example C The procedure of Example A is again repeated employing as the nonionic surface active agent a dinonyl phenol plus 5 mols ethylene oxide (40% ethylene oxide content).

Example D The procedure of Example A is once again repeated employing as the surfactant a dinonyl phenol plus 7 mols ethylene oxide (47% ethylene oxide content).

Example E The procedure of Example A is still once again re peated employing as the nonionic surface active agent dinonyl phenol reacted with 1.5 mols of ethylene oxide to yield a nonionic product containing about ethylene oxide.

Example F The above procedures are again repeated using as the nonionic precursor the condensation product of dodecyl phenol with 1.8 mol of ethylene oxide.

The chemical constitution of the products produced in the above described examples will usually be about 20 to 50% of the secondary phosphate ester of the nonionic agent, to 80% of the primary phosphate ester, and 0 to of unreacted nonionic agent.

By carrying out the above reaction in the presence of a small amount of a phosphorus-containing compound selected from the group consisting of hypophosphorous acid, salts of hypophosphorous acid, phosphorous acid, and salts and esters of phosphorous acid, preferably sodiu-rn hypophosphite or hypophosphorous acid, as described in said Nunn 057 patent, lighter colored or substantially colorless reaction products are obtained.

While the presence of unreacted nonionic is not detrimental to the attainment of the objects of the present invention, the amount of nonionic can be reduced, if desired, to a minimum of less than about 10% by incorporating in the reaction mixture a small amount of mineral acid as phosphoric acid, hydrochloric acid or sulfuric acid. Since phosphorous pentoxide yields phosphoric acid in the presence of water, the latter can advantageously and preferably be used to form the acid in situ. With the use of the mineral acid the amount of phosphorous pentoxide can also be increased to as much as 3 mols per mol of nonionic reactant, thereby favoring the formation of the monoester in major amounts, i.e., substantially no diester.

Monoesters and diesters can also be prepared from the corresponding triesters by reacting the triester with phosphoric acid. -By varying the ratio of nonionic to acid, one can prepare either monoor diester to the substantial exclusion of the other. A high ratio of triester to acid (2:1) produces diester whereas a low ratio (0.5 :1) produces monoester.

Example G Equimolar amounts of the nonionic surface active compound of Example A and phosphorous pentoxide are heated at C., while adding in the presence of about 0.4% water the P 0 over a period of one hour. Then the reaction mixture is heated for 4 hours at 125 C. The final product is a monoester.

Example H Example G is repeated employing one mol of a dodecyl phenol plus 2 mols ethylene oxide condensate and 2 mols of P 0 The final product is a monoester.

Example I Example G is again repeated using the following nonionics:

(A) octadecanol+2 mols ethylene oxide (B) hexadecanol+4 mols ethylene oxide (C) 1-eicosanol+6 mols ethylene oxide (D) l-dotriacontanol-l-7 mols ethylene oxide (E) dodecyl phenol+5 mols ethylene oxide (F) hexadecyl phenol+3 mols ethylene oxide (G) tri-n-octyl phenol+4 mols ethylene oxide (H) tri-n-octyl phenol-i-S mols propylene oxide (I) dodecyl phen0l+3 mols propylene oxide (J) dinonyl phenol+1.5 mols propylene oxide (K) diisohexyl phenol+2 mols propylene oxide (L) tri-n-butyl phenol+2 mols propylene oxide (M) tri-n-butyl phenol+3 mols propylene oxide (N) tri-n-butyl phenol+4 mols propylene oxide (0) tri-n-butyl phenol+3 mols ethylene oxide (P) hexadecanol+3 mols propylene oxide (Q) octadecanol+4 mols propylene oxide (R) butyl hexyl phenol+4 mols ethylene oxide (S) ethyl heptyl phenol+5 mols ethylene oxide (T) ethyl heptyl phenol+3 mols propylene oxide (U) ceryl alcohol-+2 mols ethylene oxide (V) l-octacosanol-l-4 mols ethylene oxide (W) l-nonacosanol-l-7 mols ethylene oxide (X) l-triacontanol-I-G mols ethylene oxide (Y) l-tetratriacontanol+5 mols ethylene oxide (Z) l-tetratriacontanol-i-Z mols propylene oxide Example I A phosphate triester of the nonionic compound of Example A is prepared by reacting 3 mols of said nonionic with 1 mol of phosphorous oxychloride in the presence of 1 mol of pyridine and ml. of benzene. The POCl is added dropwise to the other components at a temperature of about 0 C. and the temperature is held below 10 C. 'After all of the POCl has been added, the mixture is refluxed for 3 hours and then the solvent is removed under vacuum distillation. The triester results.

The triester is converted to a monoester by adding 1 mol of phosphoric acid to 0.5 mol of the triester at about room temperature. The monoester results.

Example K Example I is repeated except that 2 mols of triester are used in lieu of 0.5 mol. The diester results. i V

The monoand di-phosphated products may be represented by the following formulae:

wherein R represents H, or methyl; X may be hydrogen, alkali metal, alkaline earth meta1,'e.g.-, calcium, magnesium, barium, etc., ammonium, amine or substituted ammonium and amine, and n equals the number of mols of alkylene oxide necessary to yield a final product containing up to 50% by weight of the said alkylene oxide as discussed above; R is the alcohol or phenol hydrophobe nucleus. It is preferred that X be other flranhydrogen.

The detergents which have been used heretofore in lubricating oils are in the main metal sulfonates which, however, have only marginal performance in internal combustion engines. The phosphate estersherein-con-- templated have superior detergent properties as evidenced by the following data. In the examples which are given below, .pa-rts aretbyrweight unless otherwise indicated. These examples are by way of illustration onlyand are not to be deemed limitative of the present invention.

. ylExample 1 The oil used in the detergency test is a standard S.A.E. 20 oil which has 'been used 2000 miles and which contains no'additives. The sediment in the oil is given milliliters and the ratings are:

l-0.05 ml .=excellent 2-0.3 ml. =average 3-3 ml.=poor The physical appearance of. the supernatantoil is reported as follows:

Example 2 The outstanding anti-wear properties of the compositions of the present invention are demonstrated on the Shell Four Ball Machine (Brown-G.E. modification using 4 steel balls). The oil used is a 150 S.A.E. at 100 F. solvent refined Mid Continent oil.

TABLE II.SHELL FOUR BALL WEAR TEST [1 hour, 600 r.p.m. at 200 E] Scar siz Coeflicient of mm. friction Composition 20 kg. kg. 20 kg. 59 kg.

(A) Unmodified oil. 0. 7 0. 9 0.125 0.09 (B) (A) plus 3.3% basic barium wax benzene high boiler sulfonate 0. 6 0. 0. 10 0.005 (C) (A) plus 3.3% basic calcium dinonyl naphthalene sulfonate 0. 65 0. 0. 12 0. 09 plus 3.3% barium salt of complex phosphate ester of dinonyl phenol plus 4 mols ethylene oxide of Example A 0. 26 0. 35 0. 072 0.052 (E) (A) plus 3.3% barium salt of complex phosphate ester of dodecyl phenol plus 2 mols ethylene oxide of Example Example 3 The barium salt of the phosphate ester is prepared in general by heating the compounds of Formulae I and II preferably in the form of the free acid with barium hydroxide in mineral oil. Thus, 100 grams of a complex phosphate ester of dinonyl phenol containing 40% ethyl ene oxide (as the free acid form) is heated with agitation at C. with grams of second solvent and refined neutral mineral oil. Then 34 grams of solution in isopropanol.

Example 4- Percent E1720 on wt. of

non-ionic Mols EtzO produced TABLE I.-DETERGENCY TEXT Percent Oil wt: appear- Sediadditive ance ment ('1) Oil (no additive)- 3 3 (2) (1) plus basic barium wax benzene hi h boiler sulfonate 3. 3 2 2 (3) 1) plus basic calcium dinonyl naphthalene sulfonate 3. 3 2 2 (4) (1) plus barium salt of complex phosphate ester of dinonyl phenol plus 4 mols ethylene oxide of Example A 3. 3 1 1 (5) (1) plus barium salt of complex phosphate ester of dodecyl phenol plus 2 mols ethylene oxide of Example B 3. 3 1 1 Excellent results are obtained with the barium salts of the complexes.

In the following examples Example 2 is repeated using the indicated non-ionics. The salts thereof are also indicated.

Mols Alkylene alkylene percent Non-ionic oxide oxide Salt Example: (a) Ba.

6 Nonyl phenolethyleneoxide I 1 16.7 (b) (d) Ethylamine.

(a) Ba. 7 .-do 5 50 (d) Monoethanolamine.

(a) Ba (b) Zn 8 Dodecyl phenolethylene oxide 1.8 23. 2 gfi (amine (e) Monoethanolamine. (t) Diethylene triamine.

9 Nonyl phenolpropylene oxide 3. 0 44 g:

(a) Ca. 10 Hexadecyl phenolethylene oxide 3.0 30 fi (d) Ethylenediamlne.

n tri-n-Butylphenolethylene oxide 3.0 as {85 (a) B8. 12 tri-n-Butyl phenolpropyleue oxide..... 2. 0 31 (b) Mg.

l (a) Zn. 13 Hexadecanolethylene oxide 4. 0 42 (b) Ba. (0) Ca.

14 Octadecanolpropylene oxide 4. 0 46 (d) Zn.

The above non-ionics are phosphated before salt formation using the techniques of Example A.

Example 15 A monoester as in Example G is used as in Example 2 as the barium salt. Comparable results are achieved.

Example 16 A diester of the dinonyl phenol+7 ethylene oxide condensate (see Pat. No. 2,853,471) in the form of the barium salt is tested as in Example 2. Similar outstanding results are obtained.

Example 17 about 45% diester, about 35% monoester and about 20% unreacted non-ionic.

Examples 18-23 Example 17 is repeated using the following ratios of non-ionic to P 0 Percent Percent Ratio monoester diester Example 24 p 50 The Four-Ball wear test of Example 2 is repeated ;using the indicated compounds and conditions:

Conditions: 1 hourl00 rpm. at 250 F. Base oil: solvent refined, 100 SUS, neutral Load 40 kg. kg. 100 kg Cone Compound percent S.D. 0.0.F 2 S D C.O F SD (3.0 F.

(a) Base oil 0. 50 0. 14 0.60 0. 18 0. 75 0. 14 (b) Ex. A but 1.8 mols E.O. 1. 0 0.35 0. 100 0. 40 0. 085 0. 0. 094 (0) Same as (b) but barium salt. 1. 0 0.50 0. 105 0. 6O 0. 082 0. 65 0. 086 (d) Ex. D 1. 0 0. 45 0. 123 0. 60 0. 098 0. 50 0.110 (e) Ba salt of EX. D 1. 0 0. 60 0. 082 0. 60 0. 090 0. 65 0. 089 (I) Basic Ba salt of Ex. D 1. 0 0. 50 0. 117 0. 60 0. 078 0. 0. 089 (g) Chlorinated araffin wax (40% C1) 2. 0 0. 50 0. 053 0. 62 0. 062 0. 64 0. 080 (h) Trilauryltrithio phosphate 2. 0 0. 50 0. 097 0. 0. 094 (i) Tricresyl phosphate r 2. 0 0. 55 0. 088 0. 60 0. 098

l Scar diameter (mm.). 2 Ooefiicient of friction. a Ethylene oxide.

4 Welded.

10 Example 25 The product of Example 24(c) is tested in the follow- Elfiggf; ing composition in a MS-Sequence I, II, and III (Oldsu mobile) nfiifai Composition 5 5 ,33 B i]; SA 1Q 3 at 250 lbs. Pin appearance Solvent: Refined Mid-Continent Product base oil:

3 Very smooth, shiny. Percent by volume 3 Do. Product of Ex. 24 0 1.3 g 33; Shim Zinc dihexyl dithiophosphate (8% P; 16.1% S; 9 Slight ridgi'ng, shiny. 818% Zn) Commercial 011A 320 Severe chewing, black. V.I improver (polyalkylmethacrylate) 450 1 Each tooth is equivalent to 0.000056 inch wear.

The performance levels (based on a 0 to 10 scale with Example 7 10 being prefect) are: Varnish deposit: B-lO-A oxidation corrosion test is run on the indi- Piston skirts Aug. 95 cated products using the following setup. Rocker arm cover plate 95 Into a 100 ml. test tube, there are placed, sanded and Top cover 95 solvent cleaned:

$ (1) coil or mild steel SAP-1010 Wire 2%" long and /z in diameter; (2) 4" long piece of copper Wire 0.1 mm. in diameter Varmsh average bent double and placed half inside and half outside Sludge deposit: steel coil; and

Rocker arm plate 10.0 (3) 3 long piece of aluminum Wire 0.2 mm, in diameter Top cover 10.0 bent double and placed inside steel coil Oil screen 10.0 crankcase Oil P 9 Liquid to be tested is added to cover all metal and then a glass tube 0.4 mm. in diameter and 9% long is placed Average Sludge into test tube and a glass cover with hole in center to ac- Ring evaluation: commodate glass tube isplaced to rest on top of test tube Ring Sticking None w1th glass tube centered in test tube through hole 1n cover. on ringplugging None This setup 1s placed 1n an 011 bath at 250 F. with the oil lever being above the level of the test liquid. An air scuffing: supply running through a silica drying filter and control Valve hfter None manifold is fed to the glass tube. Air flow is 10 liters/hour Cam lobes None and test is run for 72 hours.

Example 26 In the table the numerical values for sludge and discol- The product of (a) Example D (phosphated dinonyl oratlon have the followmg slgmficance: phenol-F7 mols ethylene oxide condensate) and (b) a Sludge rating: tallow alcohol (C unsaturated)+2 mols ethylene (1) No sludge oxide condensate phosphated similarly as in Example D 45 (2) Trace sludge are tested on a Falex Wear Test apparatus in a (3) Medium sludge SUS parafiinic base oil. (4) Severe sludge Conditions: Load-1000 lbs. Discoloration scale: Time: 2 minutes each at 250, 50-0, and 750 lbs. and 15 1) No staining minutes at 1000 lbs. 50 (2) Slight staining Speed: 290 r.p.m. (3) Medium staining Temperature: F. (4) Severe staning TABLE Discoloration Sludge Composition rating Cu Al Fe Base oil plus 3% Ba salt of trideeyl alcohol plus 3 E.O.

phosphated as in Ex. A plus 0.75% zinc dihexyldithiophosphate Base oil plus 5% ssert'ae'aaei eliminate? phosphated as in Ex. A plus 0.75% zine dihexyl- Base oil plus 3% barium saii'r'iniiii Eli phosphated as in Ex. A plus 0.75% zine dihexyl dithiophosphate 4 4 4 4 1 1 Example 28 The barium salt prepared in Example 3 is compounded (A) with a typical engine oil as follows:

To the solvent refined base there is added 3.3% barium salt of Example 3, 0.75% zinc dialkyl dithiophosphate art can be made in this invention without departing from the scope or spirit thereof.

We claim:

1. A mineral lubricating oil composition containing from about 0.5% to about 25% by weight based on the and 6.6% Acryloid 966 (copolymer of lauryl meth 5 welght of the 011 of a phosphate ester, 1n the form of acrylate (90% and vinyl pyrrolidone A Similar its free acld or alkali metal, alkaline earth metal or amcomposition (B) is prepared except that the detergent z Salt of an oxyailkylene ether of an orgamc hyused is 33% of the barium salt of Wax benzene high roxy compound containing at le ast carbon atoms and boiler sulfonate. In a Shell Four Ball Text as previously 10 l from. the grollp conslstmg alkylphenols and described the results aliphatic straight chaln alcohols, sald phosphate ester being selected from the group consisting of monoesters,

diesters and mixtures thereof, said oxyalkylene ether con- SW51 taining at least one oxyalkylene group of 2 to 3 carbon k 50 kg. r atoms and a maximum of 50% by weight of oxyalkylene Composition, groups, each of from- 2 to 3 carbon atoms, based on g gg-g the weight of said oxyalkylene ether.

"""""" 2. A composition as defined in ciaim 1 wherein said organic hydroxy compound is an alkylphenol. Exam? 1e 29 3. A composition as defined in claim 1 wherein said Example 24 is repeated using 3% by weight based on 20 organic hydroxy compound is an aliphatic straipht chain the Weight of the base oil of the following amine salts: alcohol.

Mols Alkylene alkylene oxide. Phosphation Non-ionic oxide percent procedure Amine Nonyl phenol ethylene oxide 5 50 Example A... Monoethanolamine.

Do 1 .7 do Ethylamine. Dodeeyl phenolethylene 1.8 Ethylenediamine.

Do 1.8 Monoethanolemine.

D0 1.8 Diethylenetriamine. Hexadiecyl phenolethylene 3.0 Ethylenediamine. He iie tanolethylene oxide. 4.0 42 do Triethylenediamine.

Excellent anti-wear properties are evidenced by the low 4. A composition as defined in claim 1 wherein said scar diameters produced. oxyalkylene groups are oxyethylene groups.

The amine salts are prepared preferably in the mineral 5. A composition as defined in claim 1 wherein said oil base using, in general, sufficient amine to neutralize phosphate ester is employed in the form of its free acid. the acid group of the phosphate non-ionic compound. 6. A composition as defined in claim 1 wherein said All of the salts contemplated herein may also be prophosphate ester is employed in the form of its alkali duced in any suitable non-reactive solvent medium or metal salt. even in the absence of a solvent or diluent, e.g., where 7. A composition as defined in claim 1 wherein said the amine is a liquid. phosphate ester is employed in the form of its alkaline earth metal salt. Examp 1e 30 8. A composition as defined in claim 1 wherein said In a FaleX Wear Test Carried Out as in Example phosphate ester is employed in the form of its ammonium the products of Example 29, at concentrations of 0.5 l and 1% by weight based on the weight of the oil all Reference Cit d iggvresd) ibtofiigf teeth failed to be less than 10 during UNITED STATES PATENTS As described above, the usual additives may be em- 2,848,414 8/1958 Chenicek ployed with the improved detergent oils herein disclosed. 2,961,408 11/1960 y y a1 These include viscosity index improvers such as polyiso- 3,033,889 5/1962 Chlddlx et but lene, pour oint depressants, blooming agents, peptizing agents, othgr detergents, anti-oxidants and the like. PATRICK GARVIN Pnmal'y Exammer The concentration of phosphate ester in the mineral I VAUGHN, A i t t E i lubricating oils may range from about 0.5% to about 25% by weight based on the weight of the oil. U,S. Cl. X.R.

Other variations in and modifications of the described 252-493 processes which will be obvious to those skilled in the 

